US20030166958A1 - Preparation method of alkyldichlorosilanes - Google Patents
Preparation method of alkyldichlorosilanes Download PDFInfo
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- US20030166958A1 US20030166958A1 US10/335,084 US33508402A US2003166958A1 US 20030166958 A1 US20030166958 A1 US 20030166958A1 US 33508402 A US33508402 A US 33508402A US 2003166958 A1 US2003166958 A1 US 2003166958A1
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- chloride
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- hydrogen chloride
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- 238000002360 preparation method Methods 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 89
- 239000000203 mixture Substances 0.000 claims abstract description 56
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 55
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 55
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 50
- 239000010703 silicon Substances 0.000 claims abstract description 45
- 239000010949 copper Substances 0.000 claims abstract description 32
- 150000001348 alkyl chlorides Chemical class 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 239000003426 co-catalyst Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- BCJVBDBJSMFBRW-UHFFFAOYSA-N 4-diphenylphosphanylbutyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 BCJVBDBJSMFBRW-UHFFFAOYSA-N 0.000 claims description 2
- 239000005749 Copper compound Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 150000001880 copper compounds Chemical class 0.000 claims description 2
- XXECWTBMGGXMKP-UHFFFAOYSA-L dichloronickel;2-diphenylphosphanylethyl(diphenyl)phosphane Chemical compound Cl[Ni]Cl.C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 XXECWTBMGGXMKP-UHFFFAOYSA-L 0.000 claims description 2
- ZBQUMMFUJLOTQC-UHFFFAOYSA-N dichloronickel;3-diphenylphosphaniumylpropyl(diphenyl)phosphanium Chemical compound Cl[Ni]Cl.C=1C=CC=CC=1[PH+](C=1C=CC=CC=1)CCC[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 ZBQUMMFUJLOTQC-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- XGCDBGRZEKYHNV-UHFFFAOYSA-N 1,1-bis(diphenylphosphino)methane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)C1=CC=CC=C1 XGCDBGRZEKYHNV-UHFFFAOYSA-N 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000000047 product Substances 0.000 description 55
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 46
- 238000002156 mixing Methods 0.000 description 22
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 22
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 description 16
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 15
- 239000007795 chemical reaction product Substances 0.000 description 14
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 description 14
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 238000009826 distribution Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- NDTCXABJQNJPCF-UHFFFAOYSA-N chlorocyclopentane Chemical compound ClC1CCCC1 NDTCXABJQNJPCF-UHFFFAOYSA-N 0.000 description 11
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- 229940050176 methyl chloride Drugs 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 6
- 239000005052 trichlorosilane Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- HAKOAQCVDUCPTM-UHFFFAOYSA-N dichloro(propan-2-yl)silane Chemical compound CC(C)[SiH](Cl)Cl HAKOAQCVDUCPTM-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 4
- 125000006519 CCH3 Chemical group 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 4
- 229940045803 cuprous chloride Drugs 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229940038926 butyl chloride Drugs 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical class C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 3
- JANCCRMYGITTKD-UHFFFAOYSA-N dichloro(cyclopentyl)silane Chemical compound Cl[SiH](Cl)C1CCCC1 JANCCRMYGITTKD-UHFFFAOYSA-N 0.000 description 3
- NYKYPUSQZAJABL-UHFFFAOYSA-N dichloro(hexyl)silane Chemical compound CCCCCC[SiH](Cl)Cl NYKYPUSQZAJABL-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- FCMZRNUHEXJWGB-UHFFFAOYSA-N trichloro(cyclopentyl)silane Chemical compound Cl[Si](Cl)(Cl)C1CCCC1 FCMZRNUHEXJWGB-UHFFFAOYSA-N 0.000 description 3
- LFXJGGDONSCPOF-UHFFFAOYSA-N trichloro(hexyl)silane Chemical compound CCCCCC[Si](Cl)(Cl)Cl LFXJGGDONSCPOF-UHFFFAOYSA-N 0.000 description 3
- GPWLZOISJZHVHX-UHFFFAOYSA-N trichloro(propan-2-yl)silane Chemical compound CC(C)[Si](Cl)(Cl)Cl GPWLZOISJZHVHX-UHFFFAOYSA-N 0.000 description 3
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- SJTARAZFCVDEIM-UHFFFAOYSA-N dichloro(propyl)silane Chemical compound CCC[SiH](Cl)Cl SJTARAZFCVDEIM-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000011863 silicon-based powder Substances 0.000 description 2
- ABPBVCKGWWGZDP-UHFFFAOYSA-N 1,2-dichloro-3,3,4,4,5,5-hexafluorocyclopentene Chemical compound FC1(F)C(Cl)=C(Cl)C(F)(F)C1(F)F ABPBVCKGWWGZDP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- LDIKOFWFRUITPC-UHFFFAOYSA-N bis(dichlorosilyl)methyl-dichlorosilane Chemical compound Cl[SiH](Cl)C([SiH](Cl)Cl)[SiH](Cl)Cl LDIKOFWFRUITPC-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- DBKNQKMXXOSIOX-UHFFFAOYSA-N butyl(dichloro)silane Chemical compound CCCC[SiH](Cl)Cl DBKNQKMXXOSIOX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- NJKDOKBDBHYMAH-UHFFFAOYSA-N dibutyl(dichloro)silane Chemical compound CCCC[Si](Cl)(Cl)CCCC NJKDOKBDBHYMAH-UHFFFAOYSA-N 0.000 description 1
- ILZIHGWXTARXAO-UHFFFAOYSA-N dichloro(dichlorosilylmethyl)silane Chemical compound Cl[SiH](Cl)C[SiH](Cl)Cl ILZIHGWXTARXAO-UHFFFAOYSA-N 0.000 description 1
- UOZZKLIPYZQXEP-UHFFFAOYSA-N dichloro(dipropyl)silane Chemical compound CCC[Si](Cl)(Cl)CCC UOZZKLIPYZQXEP-UHFFFAOYSA-N 0.000 description 1
- KGTZBTUOZOIOBJ-UHFFFAOYSA-N dichloro(ethenyl)silicon Chemical compound Cl[Si](Cl)C=C KGTZBTUOZOIOBJ-UHFFFAOYSA-N 0.000 description 1
- MJVFSDBAXDCTOC-UHFFFAOYSA-N dichloro(prop-2-enyl)silicon Chemical compound Cl[Si](Cl)CC=C MJVFSDBAXDCTOC-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000001369 organodichlorosilanes Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- -1 reactor Substances 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
- C07F7/16—Preparation thereof from silicon and halogenated hydrocarbons direct synthesis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
- C07F7/121—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20
- C07F7/126—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20 by reactions involving the formation of Si-Y linkages, where Y is not a carbon or halogen atom
Definitions
- the present invention relates to a preparation method of alkyldichlorosilanes by directly reacting metallic silicon with a mixture of alkyl chloride having 3 or more carbon atoms and hydrogen chloride or alkyl chlorides which can generate hydrogen chloride at a reaction temperature in the presence of copper catalyst.
- reaction rate and the purity of products depend on a large number of factors, e.g., the purity of the starting materials, the type of the catalyst and amount of the catalyst used, co-catalyst, the reaction temperature and pressure, the type of reactor used, the degree of silicon conversion etc.
- the reaction conditions for the methyl chloride reaction have been well established to obtain a title compound effectively.
- the direct reaction of other alkyl chlorides than methyl chloride with metallic silicon has never been practiced on a large scale due to the decomposition of alkyl chlorides.
- propyldichlorosilane and butyldichlorosilane indicates that the alkyl chlorides decomposed under the reaction conditions to give hydrogen chloride, and the alkyl chloride and hydrogen chloride simultaneously reacted with the same silicon atom.
- organodichlorosilanes having Si—H bond could be obtained when a mixture of organic chlorides other than methyl chloride and hydrogen chloride is reacted with elemental silicon due to the reaction of both organic chloride and hydrogen chloride with the same silicon atom.
- organodichlorosilanes having Si—H bond could be obtained when a mixture of organic chlorides other than methyl chloride and hydrogen chloride is reacted with elemental silicon due to the reaction of both organic chloride and hydrogen chloride with the same silicon atom.
- one mole of methylene chloride and two moles of hydrogen chloride react with a same silicon atom to give bis(dichlorosilyl)methane (Jung et al., U.S. Pat. No. 5,235,083 (Aug. 10, 1993)).
- an object of the present invention is to provide a method for preparing alkyldichlorosilanes in a higher yield by directly reacting a mixture of alkyl chlorides and hydrogen chloride with metallic silicon.
- Another object of the present invention is to provide a method for simultaneously preparing alkyldichlorosilanes and alkyltrichlorosilanes.
- the present invention is to provide a method for preparing alkyldichlorosilanes (Formula 3) having a Si—H bond in a higher yield by directly reacting a mixture of alkyl chloride (Formula 1) having three or more carbon atoms and hydrogen chloride or alkyl chlorides (Formula 2) which can generate hydrogen chloride at a reaction temperature with metallic silicon in the presence of copper catalyst (Scheme 1).
- R is a linear, branched or cyclic C 3-10 of alkyl group.
- R 1 is hydrogen or C 4-6 alkyl group.
- Specific examples of the alkyl chloride which can generate hydrogen chloride at a reaction temperature include n-butyl chloride, t-butyl chloride and cyclohexyl chloride.
- the present invention is to provide a method for preparing alkyldichlorosilanes of Formula 3 by directly reacting a mixture of alkyl chloride and hydrogen chloride or alkyl chloride of Formula 2 which generates hydrogen chloride due to decomposition during the reaction, with metallic silicon using a fluidized bed reactor or a stirred reactor equipped with a spiral band agitator at the temperature between 200 and 350° C.
- alkyltrichlorosilanes of Formula 4 to be a raw material of silicate can be additionally obtained by the reaction.
- Linear, branched or cyclic C 3-10 alkyl chloride of Formula 1 and hydrogen chloride or alkyl chloride of Formula 2 can be mixed under the gas state with metallic silicon, or a compound of Formula 2 can be incorporated and mixed to the compound of Formula 1 in the liquid state.
- the compounds of Formula 1 and Formula 2 may be mixed with any ratio by weight or by volume. Generally, the is amount of Formula 3 compound in the products increases with increase of Formula 2 compound addition.
- the compound of Formula 2 may be mixed with alkyl chloride of Formula 1 in the mole ratio of 0.1 ⁇ 8:1, and more preferably 1 ⁇ 7:1 in order to increase a yield of the Formula 3 compound.
- a reactor used in the present invention is preferably a stirred reactor or fluidized bed reactor, and the reaction may be performed in batch operations or in a continuous process.
- Commercial silicon having a purity of 95% or more, and preferably 98% or more may be used as the elemental silicon.
- the size of the silicon powder which is proper for the reaction is preferably from 1 to 325 mesh, but the proper size and distribution of the silicon powder depend on the size and shape of the reactor. When a stirred reactor is used, the size of the powder may be 20 ⁇ 325 mesh, and more desirably 50 ⁇ 240 mesh.
- the direct reaction according to the present invention may be carried out at the various reaction temperatures ranging from 200 to 350° C., but more preferably from 200 to 300° C.
- the suitable reaction pressure may be between the atmospheric pressure and 5 atm, wherein the higher the pressure is, the faster the reaction speed becomes.
- Metal copper or copper compound which can liberate copper in the reaction condition may be used.
- the used amount of copper may be 1 to 20% by weight for the weight of reaction materials, and preferably 5 to 10% by weight.
- a co-catalyst is additionally used in an amount of 0.001 to 2% by weight for the weight of copper, the reaction becomes more faster or the selectivity for the specific product may be increased.
- Specific examples of co-catalyst to be proper for the reaction are given as follows, but the present invention is not limited by the examples. For instance, metal of Ni, Cd, Sn, Zn, Ca, Al, Mn, Mg, Ag, Cr and the like, or metal compounds which generate the above metals under the reaction condition may be used as the co-catalyst.
- the temperature of the reactor was lowered to the desired reaction temperature after contact mixture was generated, a predetermined amount of co-catalyst was-incorporated into the head of the reactor, and then the resultant material was stirred, mixed well and reacted.
- reaction products were analyzed by using gas chromatography (packed column, 10% OV 101, 1.5 m ⁇ 1/8′′ O.D., SS, TCD) and fractionally distilled to separate its constituents from one another, so that their structures could be determined.
- the structure of each constituent was determined by using a nuclear magnetic resonance spectrometer.
- the reaction products contained 8.2 g (54.7%) of 1,1-dichloro-2-methyl-1-silapropane and 0.3 g (1.7%) of 1,1,1-trichloro-2-methyl-1-silapropane.
- Other by-products were 5.8 g of trichlorosilane and unconfirmed materials.
- Table 5 shows the product compositions obtained by reacting a mixture of 2-chloropropane and t-butyl chloride with metallic silicon, only with changing the mixing ratio of 2-chloropropane and t-butyl chloride. TABLE 5 Mixing ratios of 2-chloropropane and t-butyl chloride and product distributions Total amount Product 2-chloropropane: of Yield Exp. t- products (%) No. butyl chloride (g) III a IV a 19 1:1 13.6 38.8 4.1 20 1:3 30.1 66.1 7.2 21 1:5 41.4 47.8 9.7
- reaction was carried out under the same condition as in Example 3, except that the same amount of t-butyl chloride was used as the hydrogen chloride source.
- a mixture of cyclopentyl chloride and t-butyl chloride having the mixing ratio of 1:2 was reacted with metallic silicon at 280° C. to give 30.1 g of reaction products.
- the reaction products contained 6.2 g (39.1%) of cyclopentyldichlorosilane and 0.3 g (1.6%) of cyclopentyltrichlorosilane. There were not starting materials unreacted.
- As other by-products 3.7 g (58.4%) of cyclopentene, 2.9 g of trichlorosilane and unconfirmed materials were obtained.
- Table 9 shows the product compositions obtained by reacting a mixture of cyclopentyl chloride and t-butyl chloride with metallic silicon, only with changing the mixing ratios of cyclopentyl chloride and t-butyl chloride. TABLE 9 Mixing ratios of cyclopentyl chloride and t-butyl chloride and product distrinutions Product Cyclopentyl Total amount Yield Exp. chloride: of products (%) No. t-butyl chloride (g) III b IV b cyclopentene 39 1:0.5 9.4 36.2 1.6 33.2 40 1:1 11.4 34.2 2.9 51.6 41 1:2 16.1 39.1 1.6 58.4 42 1:3 18.8 32.3 1.5 65.4
- Table 13 shows the product compositions obtained by reacting a mixture of 1-chlorohexane and t-butyl chloride with metallic silicon, only with changing the mixing ratio of 1-chloropropane and t-butyl chloride. TABLE 13 Mixing ratios of 1-chlorohexane and t-butyl chloride and product distributions Total 1- amount chlorohexane: of Prod- Product Yield (%) Exp. t- uct 1- No.
- butylchloride (g) chlorohexane III c IV c hexene 61 1:2 9.5 6.5 36.3 7.1 12.8 62 1:4 13.2 7.5 43.7 8.9 15.3 63 1:6 16.1 13.2 45.2 9.0 17.9 64 1:8 12.3 13.1 29.9 5.8 8.2
- alkyldichlorosilanes prepared in accordance with the present invention can addtionally react with an organic compound having an unsaturated bond, they may be an important starting materials in preparing an organosilicon compound having various organic functional groups, and will be useful for the manufacture of silicones.
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Abstract
Description
- 1. Field of the Invention
- The present invention relates to a preparation method of alkyldichlorosilanes by directly reacting metallic silicon with a mixture of alkyl chloride having 3 or more carbon atoms and hydrogen chloride or alkyl chlorides which can generate hydrogen chloride at a reaction temperature in the presence of copper catalyst.
- 2. Description of the Background Art
- Since a preparation method of methylchlorosilanes by directly reacting metallic silicon with methyl chloride in the presence of copper catalyst was introduced in the U.S. Pat. No. 2,380,995, the synthesis of organosilicon compound in the current silicon industry is mostly based on the above skill. In the above reaction, a number of high boiling materials besides methylchlorosilanes are also obtained in small quantity. Also because the reaction rate and the purity of products depend on a large number of factors, e.g., the purity of the starting materials, the type of the catalyst and amount of the catalyst used, co-catalyst, the reaction temperature and pressure, the type of reactor used, the degree of silicon conversion etc., the reaction conditions for the methyl chloride reaction have been well established to obtain a title compound effectively. But still, the direct reaction of other alkyl chlorides than methyl chloride with metallic silicon has never been practiced on a large scale due to the decomposition of alkyl chlorides.
- In 1955, Petrov and his co-workers reported the direct reactions of propyl chloride or butyl chloride with metallic silicon (A. D. Petrov, N, P. Smetankina, and G. I. Nikisshin. J.Gen.Chem. USSR, 1955, 25, 2305) and obtained propyldichlorosilane or butyidichlorosilane having a Si—H bond in low yields, but not dipropyldichlorosilane or dibutyldichlorosilane. The production of propyldichlorosilane and butyldichlorosilane indicates that the alkyl chlorides decomposed under the reaction conditions to give hydrogen chloride, and the alkyl chloride and hydrogen chloride simultaneously reacted with the same silicon atom.
- Also, Yoshio Ono and his co-workers reported that vinyldichlorosilane or isopropyldichlorosilane could be synthesized by reacting a mixture of ethylene or propylene and hydrogen chloride with elemental silicon, but the yield was low. They also reported that isopropyldichlorosilane and normal prodichlorosilane could be obtained by reacting a mixture of propylene and hydrogen chloride with activated silicon contact mixture containing 3% by weight of copper at 500° C. for 10 minutes (M. Okamoto, S. Onodera, Y. Yamamoto, E. Suzuki, Y. Ono, J.Chem.Soc., Dalton Trans., 2001. 71-78).
- The present inventors found that organodichlorosilanes having Si—H bond could be obtained when a mixture of organic chlorides other than methyl chloride and hydrogen chloride is reacted with elemental silicon due to the reaction of both organic chloride and hydrogen chloride with the same silicon atom. For instance, when a mixture of methylene chloride and hydrogen chloride is reacted with silicon, one mole of methylene chloride and two moles of hydrogen chloride react with a same silicon atom to give bis(dichlorosilyl)methane (Jung et al., U.S. Pat. No. 5,235,083 (Aug. 10, 1993)). When a mixture of chloroform and hydrogen chloride is reacted with silicon, one mole of chloroform and three moles of hydrogen chloride react with a same silicon atom to give tris(dichlorosilyl)methane (Jung et al., U.S. Pat. No. 5,332,849(Jul. 26, 1994)). Similarly, when a mixture of allyl chloride and hydrogen chloride is reacted with silicon, one mole of allyl chloride and one mole of hydrogen chloride react with a same silicon atom to give allyldichlorosilane (Jung et al., U.S. Pat. No. 5,338,876 (Aug. 16, 1994)). In the above reactions, the decomposition of starting organic chloride was suppressed and products having Si—H bonds were obtained by adding hydrogen chloride as a raw material. Alkyl chlorides which can generate hydrogen chloride by decomposition at the reaction temperature could be also used instead of hydrogen chloride.
- In a direct reaction of metallic silicon and organic chloride, it is well known that the reactions do not proceed without catalysts, and the preferred catalyst is copper. If necessary, metals as Zn, Al, Cd and the like can be used as a co-catalyst. If the amount of the copper catalyst is increased, the reaction becomes faster but the content of chlorine in products increases. Therefore, copper is generally used in about 10% or less by weight for the weight of silicon in the reaction of silicon and methyl chloride, On the other hand, when methyl chloride was directly reacted with silicon, if metal complex of organic phosphin was added, methylchlorosilanes could be synthesized in a higher yield with an excellent selectivity (S. Ueno, T. Shinohara, M. Aramata, Y. Tanifuji, T. Inukai, K. Fujioka, U.S. Pat. No. 6,215,012(Oct. 4, 2001)). Also, since the reaction of silicon with alkyl chloride was an exothermic reaction, if the heat of reaction could not be efficiently controlled, or if a proper reaction temperature was not maintained, the reaction materials were coagulated and a partly overheated state was formed (A. L. Klebamskii and V. S. Fikhtengolts, J. Gen. Chem. U.S.S.R, 1957, 27, 2693). Furthermore, it was reported that a excessively high reaction temperature gave more by-products as well as the preferred alkyldichlorosilanes, thereby alkyl chlorides of starting materials and products were decomposed causing the deposition of carbon on the surface of silicon, and accordingly activity of silicon was rapidly decreased (J. C. Vlugter, and R. J. H. Voorhoeve, Conf. Accad. Lincei, Alta Tech. Chim. 1962, 81).
- The common disadvantage of these methods arises from the facts that since the composition of the products are largely affected by the reaction condition, this condition must be carefully determined to obtain the desired products effectively; economic efficiency is degraded by the low yield; and raw materials are rapidly decomposed to give much amount of by-products. The present inventors of the invention have studied a method for preparing alkyldichlorosilanes in a higher yield with restraining generation of the by-products. As a result, the present inventors found an improved method for preparing alkyldichlorosilanes by directly reacting metallic silicon with a mixture of alkyl chloride and hydrogen chloride or alkyl chlorides which can generate hydrogen chloride at the reaction temperature.
- Therefore, an object of the present invention is to provide a method for preparing alkyldichlorosilanes in a higher yield by directly reacting a mixture of alkyl chlorides and hydrogen chloride with metallic silicon.
- Another object of the present invention is to provide a method for simultaneously preparing alkyldichlorosilanes and alkyltrichlorosilanes.
- The foregoing and other objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description and examples of the present invention.
- The present invention is to provide a method for preparing alkyldichlorosilanes (Formula 3) having a Si—H bond in a higher yield by directly reacting a mixture of alkyl chloride (Formula 1) having three or more carbon atoms and hydrogen chloride or alkyl chlorides (Formula 2) which can generate hydrogen chloride at a reaction temperature with metallic silicon in the presence of copper catalyst (Scheme 1).
- RCl (Formula 1)
- R1Cl (Formula 2)
- RSiHCl2 (Formula 3)
- RSiCl3 (Formula 4)
- RCl+R1Cl RSiHCl2+RSiCl3 (Scheme 1)
- Wherein, R is a linear, branched or cyclic C3-10 of alkyl group. R1 is hydrogen or C4-6 alkyl group. Specific examples of the alkyl chloride which can generate hydrogen chloride at a reaction temperature include n-butyl chloride, t-butyl chloride and cyclohexyl chloride.
- More specifically, the present invention is to provide a method for preparing alkyldichlorosilanes of Formula 3 by directly reacting a mixture of alkyl chloride and hydrogen chloride or alkyl chloride of Formula 2 which generates hydrogen chloride due to decomposition during the reaction, with metallic silicon using a fluidized bed reactor or a stirred reactor equipped with a spiral band agitator at the temperature between 200 and 350° C. Also, alkyltrichlorosilanes of Formula 4 to be a raw material of silicate can be additionally obtained by the reaction.
- Linear, branched or cyclic C3-10 alkyl chloride of Formula 1 and hydrogen chloride or alkyl chloride of Formula 2 (which is decomposed during the reaction and generates hydrogen chloride) can be mixed under the gas state with metallic silicon, or a compound of Formula 2 can be incorporated and mixed to the compound of Formula 1 in the liquid state. The compounds of Formula 1 and Formula 2 may be mixed with any ratio by weight or by volume. Generally, the is amount of Formula 3 compound in the products increases with increase of Formula 2 compound addition. The compound of Formula 2 may be mixed with alkyl chloride of Formula 1 in the mole ratio of 0.1˜8:1, and more preferably 1˜7:1 in order to increase a yield of the Formula 3 compound.
- A reactor used in the present invention is preferably a stirred reactor or fluidized bed reactor, and the reaction may be performed in batch operations or in a continuous process. Commercial silicon having a purity of 95% or more, and preferably 98% or more may be used as the elemental silicon. The size of the silicon powder which is proper for the reaction is preferably from 1 to 325 mesh, but the proper size and distribution of the silicon powder depend on the size and shape of the reactor. When a stirred reactor is used, the size of the powder may be 20˜325 mesh, and more desirably 50˜240 mesh.
- The direct reaction according to the present invention may be carried out at the various reaction temperatures ranging from 200 to 350° C., but more preferably from 200 to 300° C. Also, the suitable reaction pressure may be between the atmospheric pressure and 5 atm, wherein the higher the pressure is, the faster the reaction speed becomes.
- As the catalyst, Metal copper or copper compound which can liberate copper in the reaction condition may be used. The used amount of copper may be 1 to 20% by weight for the weight of reaction materials, and preferably 5 to 10% by weight. Provided that a co-catalyst is additionally used in an amount of 0.001 to 2% by weight for the weight of copper, the reaction becomes more faster or the selectivity for the specific product may be increased. Specific examples of co-catalyst to be proper for the reaction are given as follows, but the present invention is not limited by the examples. For instance, metal of Ni, Cd, Sn, Zn, Ca, Al, Mn, Mg, Ag, Cr and the like, or metal compounds which generate the above metals under the reaction condition may be used as the co-catalyst.
- Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited by Examples.
- 360 g (140-200 mesh) of metallic silicon, 62.4 g of cuprous chloride (CuCl) and 20 g of micro-spherical acid clay (in order to improve flowability) were mixed well and placed in a reactor. Then the mixture was dried at 250° C. for 2 hours with stirring by dry nitrogen flush. After drying, the temperature of the reactor was raised and kept at 370° C. for 3 hours to give a Si/Cu contact mixture having a high reactivity, together with tetrachlorosilane. In case Cd, Ni, Sn, Zn and the like are used as the co-catalyst, the temperature of the reactor was lowered to the desired reaction temperature after contact mixture was generated, a predetermined amount of co-catalyst was-incorporated into the head of the reactor, and then the resultant material was stirred, mixed well and reacted.
- 360 g (140-200 mesh) of metallic silicon, 40 g of copper catalyst and 20 g of micro-spherical acid clay were placed in the reactor, and dried under the condition similar to that of Example 1. After drying, the temperature of the reactor was raised to 350° C., and methyl chloride (CH3Cl) was injected through a preheating tube at the bottom of the reactor. After about 40-70 minutes, dimethyldichlorosilane and methyltrichlorosilane began to be generated as the reaction products and were collected in the receiver at the bottom of the reactor. After the reaction with methyl chloride for about 3 hours, a Si/Cu contact mixture which can be properly used for the present invention is produced. In case a co-catalyst is necessary for the reaction, it may be incorporated in the same method as Example 1. Si/Cu contact mixture having different mixing ratio of catalysts was prepared, and the compositions are shown in Table 1.
TABLE 1 Composition of Si/Cu contact mixture of the present invention Exp. Amount of Amount of copper Co-catalyst No. Si (g) type amount(g) type amount(g) remarks I-1 360 CuCl 62.4 I-2 360 Cu 40 I-3 360 Cu 40 NiCl2(dppe) 0.6 I-4 360 Cu 40 NiCl2(dppb) 0.6 I-5 360 Cu 40 NiCl2(dppp) 0.6 I-6 360 Cu 40 Sn 2 I-7 360 Cu 40 Cd 2 I-8 360 Cu 40 Zn 2 - In order to optimize the reaction temperature, the reaction was carried out as shown in the following typical experimental No. 2. 360 g of Si/Cu contact mixture (1-4) prepared in Example 2 was placed in a stirred reactor, the temperature of the reactor was raised to 220° C. and then, nitrogen gas and hydrogen chloride were flowed into the reactor and at the same time, 2-chloropropane(10 ml, 0.108 mole) was added using a syringe pump into a preheating tube of the reactor. The amount of reaction products obtained after completing the reaction was 15.1 g. The obtained reaction products were analyzed by using gas chromatography (packed column, 10% OV 101, 1.5 m×1/8″ O.D., SS, TCD) and fractionally distilled to separate its constituents from one another, so that their structures could be determined. The structure of each constituent was determined by using a nuclear magnetic resonance spectrometer. The reaction products contained 8.2 g (54.7%) of 1,1-dichloro-2-methyl-1-silapropane and 0.3 g (1.7%) of 1,1,1-trichloro-2-methyl-1-silapropane. Other by-products were 5.8 g of trichlorosilane and unconfirmed materials.
- 1,1-dichloro-2-methyl-1-silapropane
- (1H-NMR, CDCl3, ppm): 1.15 (s, 3H, CCH3), 1.17 (s, 3H, CCH3), 1.34-1.39(m, 1H, CH3CH), 5.39 (s, 1H, S1H)
- 1,1,1-trichloro-2-methyl-1-silapropane
- (1H-NMR, CDCl3, ppm):1.18 (s, 3H, CCH3), 1.20 (s, 3H, CCH3), 1.48-1.58(m, 1H, CH3CH)
- The product compositions obtained from the reactions at various reaction temperatures using the same condition (for example, starting material, reactor, catalyst, co-catalyst etc.) are shown in Table 2.
TABLE 2 Product distributions at various reaction temperatures Total Product Reaction Amount Yield Exp. temperature of products (%) No. (° C.) (g) IIIa IVa 1 200 10.1 26.0 0.7 2 220 15.1 54.7 1.7 3 250 9.7 41.3 1.8 4 270 11.3 26.7 1.6 5 300 8.9 15.5 1.4 - To study the effect of hydrogen chloride addtion, the reaction was carried out using the same contact mixture and method as described in Example 3, except engaging the mixing ratios of 2-chloropropane and hydrogen chloride at 220° C. This is to optimize the amount of hydrogen chloride at the reaction temperature of 220° C. where the yield of the products is highest. The results are shown in Table 3. However, the experimental No. 9 was conducted in a fluidized bed reactor under the same condition.
TABLE 3 Mixing ratios of 2-chloropropane and hydrogen chloride, and product distributions 2-chloropropane: Product hydrogen Total amount Yield Exp. chloride of products (%) No. (mole ratio) (g) IIIa IVa 6 1:0 8.5 34.1 2.3 7 1:1.5 10.6 37.6 2.1 8 1:2.5 15.1 54.7 1.7 9 1:2.5 9.1 28.3 2.5 10 1:3 16.6 35.6 1.9 - The reaction was conducted using contact mixtures of Table 1 under the same condition as described in experiment No. 2 of Example 3, and the results are shown in Table 4.
TABLE 4 Effect of catalyst and co-catalysts on product distributions Total Product Kind of amount of Yield Exp. contact products (%) No. mixture (g) IIIa IVa 11 I-1 2.5 5.3 — 12 I-2 9.6 42.1 7.3 13 I-3 5.3 4.3 0.1 14 I-4 15.1 54.7 1.7 15 I-5 6.4 25.0 1.3 16 I-6 0.5 — — 17 I-7 3.5 17.2 0.2 18 I-8 — — — - The present experiement was described as shown in the following typical experimental No. 20 in Table 5. The reaction was carried out under the same condition as in Example 3, except that the same amount of t-butyl chloride was used as the hydrogen chloride source. A mixture of 2-chloropropane and t-butyl chloride having the mixing ratio of 1:3 was reacted with metallic silicon to give 30.1 g of reaction products. The reaction products contained 10.2 g (66.1%) of 1,1-dichloro-2-methyl-1-silapropane and 0.66 g (7.2%) of 1,1,1-trichloro-2-methyl-1-silapropane. As one of other by-products, 13.6 g of trichlorosilane was obtained.
- Table 5 shows the product compositions obtained by reacting a mixture of 2-chloropropane and t-butyl chloride with metallic silicon, only with changing the mixing ratio of 2-chloropropane and t-butyl chloride.
TABLE 5 Mixing ratios of 2-chloropropane and t-butyl chloride and product distributions Total amount Product 2-chloropropane: of Yield Exp. t- products (%) No. butyl chloride (g) IIIa IVa 19 1:1 13.6 38.8 4.1 20 1:3 30.1 66.1 7.2 21 1:5 41.4 47.8 9.7 - In order to optimize the reaction temperature, the reaction was carried out as shown in the following typical experimental No. 23 in Table 6. Nitrogen gas was flowed into the reactor after raising the temperature of the reactor to 260° C. similarly with Example 3 and at the same time, cyclopentyl chloride (10 ml, 0.0942 mole) was added using a syringe pump into the preheating tube of the reactor. The total amount of reaction products obtained after completing the reaction was 8.1 g. The reaction products contained 3.4 g (21.4%) of cyclopentyldichlorosilane and 0.2 g (1.2%) of cyclopentyltrichlorosilane. Other by-products were 3.9 g (60.8%) of cyclopentene, 0.6 g of trichlorosilane, and minor unconfirmed materials.
- cyclopentyldichlorosilane
- (1H-NMR, CDCl3, ppm):1.47-1.93 (m, 9H, CyclicH), 5.43 (s,1H, S1H)
- cyclopentyltrichlorosilane
- (1H-NMR, CDCl3, ppm):1.56-1.95 (m, 9H, CyclicH)
- The product compositions obtained from the reactions at a various reaction temperatures using the same condition with the above-mentioned experiment are shown in Table 6.
TABLE 6 Product distributions at various reaction temperatures Total product Reaction amount of Yield Exp. temperature products (%) No. (° C.) (g) IIIb IVb cyclopentene 22 240 7.0 6.2 0.6 77.4 23 260 8.1 21.4 1.2 60.8 24 280 8.0 20.2 2.2 59.8 25 300 7.9 19.2 3.1 57.6 - To study the effect of hydrogen chloride addtion, the reaction was carried out using the same contact mixture and method as described in Example 3, except changing the mixing ratios of cyclopentyl chloride and hydrogen chloride at 260° C. The reaction results are shown in Table 7. However, the experimental No. 27 was conducted in a fluidized bed reactor under the same conditions.
TABLE 7 Mixing ratios of cyclopentyl chloride and hydrogen chloride, and product distributions Product Cyclopentyl Total amount Yield Exp. chloride: of products (%) No. hydrogen chloride (g) IIIb IVb cyclopentene 26 1:0 8.1 21.4 1.2 60.8 27 1:0 5.2 9.5 1.8 61.2 28 1:1 7.4 11.5 0.6 65.9 29 1:2 9.9 11.9 0.5 76.0 30 1:4 27.0 10.6 0.6 81.0 - The reaction was conducted using contact mixtures of Table 1 under the same condition as described in experiment No. 23 of Example 7, and the results are shown in Table 8.
TABLE 8 Eeffect of catalyst and co-catalysts on product distributions product Kind of Total amount Yield Exp. contact of products (%) No. mixture (g) IIIb IVb cyclopentene 31 I-1 2.8 2.2 0.2 28 32 I-2 4.3 5.6 0.5 34 33 I-3 5.4 4.9 0.4 54.8 34 I-4 8.1 21.4 1.2 60.8 35 I-5 4.2 12.9 0.8 7.0 36 I-6 0.7 — 3.3 — 37 I-7 2.0 8.4 0.2 5.7 38 I-8 1.1 0.3 — 6.1 - The reaction was carried out under the same condition as in Example 3, except that the same amount of t-butyl chloride was used as the hydrogen chloride source. A mixture of cyclopentyl chloride and t-butyl chloride having the mixing ratio of 1:2 was reacted with metallic silicon at 280° C. to give 30.1 g of reaction products. The reaction products contained 6.2 g (39.1%) of cyclopentyldichlorosilane and 0.3 g (1.6%) of cyclopentyltrichlorosilane. There were not starting materials unreacted. As other by-products, 3.7 g (58.4%) of cyclopentene, 2.9 g of trichlorosilane and unconfirmed materials were obtained.
- Table 9 shows the product compositions obtained by reacting a mixture of cyclopentyl chloride and t-butyl chloride with metallic silicon, only with changing the mixing ratios of cyclopentyl chloride and t-butyl chloride.
TABLE 9 Mixing ratios of cyclopentyl chloride and t-butyl chloride and product distrinutions Product Cyclopentyl Total amount Yield Exp. chloride: of products (%) No. t-butyl chloride (g) IIIb IVb cyclopentene 39 1:0.5 9.4 36.2 1.6 33.2 40 1:1 11.4 34.2 2.9 51.6 41 1:2 16.1 39.1 1.6 58.4 42 1:3 18.8 32.3 1.5 65.4 - In order to optimize the reaction temperature, the reaction was carried out as shown in the following typical experimental No. 45. The temperature of the reactor was raised to 280° C. in the same method as Example 3. Then, nitrogen gas and hydrogen chloride were flowed into the reactor and at the same time, 1-chlorohexane (10 ml, 0.072 mole) was added using a syringe pump into a preheating tube of the reactor. The amount of reaction products obtained after completing the reaction was 13.0 g. The reaction products contained 4.7 g (35.6%) of 1,1-dichloro-1-silaheptane and 0.9 g (5.5%) of 1,1,1-trichloro-1-silaheptane. Other by-products were 1.9 g (22.4%) of raw materials which were remained unreacted, 1.7 g (28.1%) of 1-hexene, 2.5 g of trichlorosilane, and unconfirmed material.
- 1,1-dichloro-1-silaheptane
- (1H-NMR, CDCl3, ppm): 0.89 (t, J=6.6 Hz, 3H, CH3), 1.17-1.56 (m, 10H, (CH2)5CH3), 5.51 (t, J=1.5 Hz, 1H, S1H)
- 1,1,1-trichloro-1-silaheptane
- (1H-NMR, CDCl3, ppm):0.92 (t, J=6.9 Hz, 3H, CH3), 1.31-1.61(m, 10H, (CH2)5CH3)
- The product compositions obtained from the reactions at a various reaction temperatures using the same condition with the above-mentioned experiment are shown in Table 10.
TABLE 10 Product distributions at various reaction temperatures Total Reaction Amount of Product Yield Exp. temperature Products (%) No. (° C.) (g) 1-chlorohexane IIIc IVc hexene 43 240 11.7 52.1 25.3 2.2 12.2 44 260 10.5 27.8 30.4 3.9 11.9 45 280 13.0 22.4 35.6 5.5 28.1 46 300 12.3 19.6 26.1 5.8 36.4 - To study the effect of hydrogen chloride addtion, the reaction was carried out using the same contact mixture and method as described in Example 3, except changing the mixing ratios of 1-chlorohexane and hydrogen chloride at 280° C. The reaction results are shown in Table 11. However, the experimental No. 52 was conducted in a fluidized bed reactor using the same conditions.
TABLE 11 Mixing ratios of 1-chlorohexane and hydrogen chloride, and product distributions Total 1- amount chlorohexane: of prod- Product Yield (%) Exp. hydrogen ucts 1- No. chloride (g) chlorohexane IIIc IVc hexene 47 1:0 5.0 12.2 14.4 4.0 16.1 48 1:2 8.9 10.9 27.7 8.8 25.0 49 1:4 8.7 5.7 29.8 11.2 21.8 50 1:8 13.0 22.4 35.6 5.5 28.1 51 1:10 18.5 10.4 41.2 6.0 30.2 52 1:10 11.3 8.5 20.7 5.2 27.8 - The reaction was conducted using contact mixtures of Table 1 under the same condition as described in experiment No. 51 of Example 12, and the results are shown in Table 12.
TABLE 12 Effect of catalyst and co-catalysts on product distributions Kind of Total amount Exp. contact of product Product Yield (%) No. mixture (g) 1-chlorohexane IIIc IVc hexene 53 I-1 12.3 — — — 46.0 54 I-2 23.4 18.5 5.6 1.5 68.4 55 I-3 32.0 — — — 98.2 56 I-4 18.5 10.4 41.2 6.0 30.2 57 I-5 31.2 — 10.2 7.2 80.6 58 I-6 3.73 12.1 2.4 5.6 11.2 59 I-7 7.37 15.3 28.2 1.9 11.1 60 I-8 5.3 12.4 0.5 — 24.6 - The present experiement was described as shown in the following typical experimental No. 63 in Table 13. The reaction was carried out under the same condition as in Example 3, except that the same amount of t-butyl chloride was, used as the hydrogen chloride source. A mixture of 2-chloropropane and t-butyl chloride having the mixing ratio of 1:6 was reacted with metallic silicon at 280° C. to give 16.1 g of reaction products. The reaction products contained 5.9 g (45.2%) of 1,1-dichloro-1-silaheptane and 1.4 g (9.0%) of 1,1,1-trichloro-1-silaheptane. As other by-products, 31.1 g (13.2%) of 1-chlorohexane which is remained unreacted, 1.1 g (17.9%) of hexene, 2.5 g of trichlorosilane, and unconfirmed materials were obtained.
- Table 13 shows the product compositions obtained by reacting a mixture of 1-chlorohexane and t-butyl chloride with metallic silicon, only with changing the mixing ratio of 1-chloropropane and t-butyl chloride.
TABLE 13 Mixing ratios of 1-chlorohexane and t-butyl chloride and product distributions Total 1- amount chlorohexane: of Prod- Product Yield (%) Exp. t- uct 1- No. butylchloride (g) chlorohexane IIIc IVc hexene 61 1:2 9.5 6.5 36.3 7.1 12.8 62 1:4 13.2 7.5 43.7 8.9 15.3 63 1:6 16.1 13.2 45.2 9.0 17.9 64 1:8 12.3 13.1 29.9 5.8 8.2 - Since alkyldichlorosilanes prepared in accordance with the present invention can addtionally react with an organic compound having an unsaturated bond, they may be an important starting materials in preparing an organosilicon compound having various organic functional groups, and will be useful for the manufacture of silicones.
- As the present invention may be embodied in several forms without departing from the spirit or essential characteristics thereof, it should also be understood that the above-described embodiments are not limited by any of the details of the foregoing description, unless otherwise specified, but rather should be construed broadly within its spirit and scope as defined in the appended claims, and therefore all changes and modifications that fall within the metes and bounds of the claims, or equivalence of such metes and bounds are therefore intended to be embraced by the appended claims.
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KR940010291B1 (en) * | 1992-01-23 | 1994-10-22 | 한국과학기술연구원 | Bis(silyl)alkanes and process for the preparation thereof |
KR950002860B1 (en) * | 1992-06-13 | 1995-03-27 | 한국과학기술연구원 | Chloroakdenylsilanes and its method of preparation |
US5332849A (en) * | 1994-01-03 | 1994-07-26 | Korea Institute Of Science And Technology | Tris(silyl) alkanes and their preparation methods |
KR100469945B1 (en) * | 1996-12-31 | 2005-04-08 | 삼성정밀화학 주식회사 | Manufacturing Method of Vinyl Chlorosilane |
-
2002
- 2002-01-30 KR KR10-2002-0005452A patent/KR100454713B1/en not_active IP Right Cessation
- 2002-12-31 US US10/335,084 patent/US6911552B2/en not_active Expired - Fee Related
-
2003
- 2003-01-24 DE DE10302792A patent/DE10302792B4/en not_active Expired - Fee Related
- 2003-01-30 JP JP2003022087A patent/JP2003238575A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3454616A (en) * | 1966-07-25 | 1969-07-08 | Shinetsu Chem Ind Co | Method for preparing monomethyldichlorosilane |
US4973725A (en) * | 1988-06-28 | 1990-11-27 | Union Carbide Chemicals And Plastics Company Inc. | Direct synthesis process for organohalohydrosilanes |
US6215012B1 (en) * | 2000-06-08 | 2001-04-10 | Shin-Etsu Chemical Co., Ltd. | Preparation of organohalosilanes |
Also Published As
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JP2003238575A (en) | 2003-08-27 |
DE10302792A1 (en) | 2003-08-07 |
KR20030065718A (en) | 2003-08-09 |
KR100454713B1 (en) | 2004-11-05 |
US6911552B2 (en) | 2005-06-28 |
DE10302792B4 (en) | 2004-05-06 |
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